CA2007957A1 - Polymeric particles product containing melanic pigments; process for preparing the same and its use in cosmetics - Google Patents

Abstract

The invention relates to a product consisting of polymer particles, chosen from the group consisting of particles of (a) polymers derived from optionally modified keratin; (b) silk fibroin; (c) polymers derived from optionally deacetylated chitin; (d) synthetic polymers chosen from the group consisting of (i) crosslinked polymethyl methacrylate, (ii) crosslinked poly-.beta.-alanine, (iii) hollow microspheres of the copolymer of vinylidene chloride and acrylonitrile, (iv) porous microspheres of polyamide 12, polyamide 6 or copolyamide 6/12, and (v) silicone powders consisting of gums, resins, organopolysiloxane elastomers. These particles have a particle size of less than 100 microns and comprise on the surface and / or in the polymer network, a natural or synthetic melanin pigment, this pigment being either formed beforehand and absorbed by the particles, or formed in situ by oxidation of a dye. indolic. The product according to the invention is used in particular in the cosmetic field, for the protection of the human epidermis against the harmful effects of solar radiation, for the make-up of the skin, of the hairs, of the eyelashes and of the eyebrows and of the coloring of the hair. .

Description

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The present invention is re: Lative to new products made of fine particles of polymer, comprising melanin pigments, at their method of preparation and their use, in particular in the field of cosmetics, for makeup hair and skin, protecting the human epidermis against UV radiation and hair coloring.
Hair, skin and hair color of human origin comes mainly from pigments ; 10 melanins secreted by melanocytes and we also know well the protective role of the pigment melani-that vis-à-vis the solar radiation.
These pigments, of natural origin, include in particular black or brown pigments which are called eumelanins.
Their natural biosynthesis takes place in several stages by polymerization of the products of oxidation of an amino acid: tyrosine and one of its ~; oxidation products is 5,6-dihydroxyindole which - 20 in turn polymerizes to eumelanlne.
We have already tried to manufacture in vitro pigments ~ based on pseudomelani ~ ne ~ or compounds similar to melanin which are non-toxic and non-toxic : ~:
allergens and ~ which are particularly interesting in make-up compositions for the skin, the hairs, eyelashes and eyebrows, for which we are looking for segments with ~ good safety compared to commonly used pigments, such as - ~
~ ~ Eer oxide base.
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The Applicant has discovered, which makes the subject of the invention, which it was possible to prepare with a good yield, a product constituted by fine particles based on special polymers from ~ inis below ~ and a melanin pigment.
Melanic pigment is called the pigment that forms by oxidation of 5,6-dihydroxyindole, possibly combines with 2-carboxy 5,6-dihydroxyindole.
. :
By analogy and simplification, we will call Also "melanin pigment" the pigment formed by oxidation of each of the compounds of formula (I) defined below.
These new products can be used in as pigments or adjuvants in various fields techniqu ~ es where; we use the use of partlcules pigmented, such as paint, :::
cosmetic, -etc.
The products according to the invention are use more ~ especially as; pigments in 20 ~ ndustrle cosmetic, especially for the protection of 1'humid epidermis against ~ harmful effects of rayon-m ~ nt ~ solalre ~; for making up the skin, hair, eyelashes and eyebrows and ~ coloring of hair.
The ~ present ~ lnv ~ ention therefore relates to a product constituted by fine particles of polymers partlculiers;, ~ comprising ~ melanlques segments.
Another object of the invention is constituted by the prep ~ aration of such a prodult.

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- The invention ~ ise also the application cosmetic of such products, especially in makeup of skin and hair (eyelashes and eyebrows ~, protection of the human epidermis against UV radiation and hair coloring.
The product according to the invention is essential characterized by the fact that it is made up of polymer particles defined below having a particle size lometry less than 100 microns and comprising, in 10 surface and / or in the polymer network, a melanin pigment natural or synthetic, formed in situ or formed before-and absorbed by the polymer particles.
; Preferably: the melanin pigment results from the oxidation of at least one indolic dye, corresponding to a.
: the formula: .
:::
:.

; (I) ~: ~: R Rl 20 ~ 7 ::; ~:
::in which:
,: ~:
Rl represents ~ a hydrogen atom or a C1-C4 alkyl group;
: R2 and R3, ldentlques or difLérents, represent tent a: ~ hydrogen atom, ~: a C1-C4 alkyl group, a ~ arboxyl group or: ~ a C1-C4 alkoxy group carbonyl ;:
; R4, R5, R6 and R7, identical or different, represent a hydrogen atom, an alkyl radical in Cl-C4, a group ~ -NHR (in which R denotes an atom , ~.
: ~ - 3 -i ~: ~
.:

213 ~ 79S7 hydrogen or C1-C4 alkyl, hydroxy-C1-C4 alkyl or C2-C6 polyhydroxyalkyl), acylamino, carboxyl, C1-C4 carboxyalkyl, C1-C4 carbonyl alkoxy, alkoxy Cl-C4 carbonylalkyl Cl-C4, carbamyl, halogen, mono- or polyhydroxy C1-C4alkyl, aminoalkyl C1-C4, an OZ group, in which Z denotes a hydrogen atom gene or a linear or branched alkyl group in Cl-C20, a C1-C4 aralkyl group, a group formyl, a linear C2-C20 acyl group or branched, a linear C3-C20 alkenoyl group or branch, a group -SiRllR12R13, a group .
-P (O) (OR8) 2, an R8OSO2- group; the radicals R4 and R5, either R5 and R6, or else R6 and R7 can form, together with the carbon atoms to which they are rattaches, a cycle possibly containing a group carbonyl ~; a thloc ~ arbonyl group,: a group = P (O1 (OR8) or a group ---- CRgRlo;
subject: provided that at least ~ one of the radicals R4 to R7 ~: represents an ~ OZ group, or blen as one of the ; 20 ~: radi ~ cals R4 to: ~ R7 represents -NHR, ~ or that ~ R4 and R5, or : well R5: and R6, or blen R6 and R7 form a cycle, R8 and Rg represent a: atom ~ of hydrogen or: ~ a group ~ aI ~ yle nfer ~ ieur in ~ Cl-C4, ~ R10 ~ represents ~; a group ~ alkoxy group ~
-C4 DU ~ a group ~ ement mono- or dl ~ alkyl ~ (Cl-C4i ~ amlno, ~ Rll, R1 ~ 2 ~ and R13, identical or ~: different, represent groups ~ alkyl ~ C1-C4, llnear ~ Qu branched; ~
or ~ a ~ of its salts ~ of ~; ~ alkali metals, aloalino-earthy, ~ ammonium: or ~ 'amines ~
Indolic dyes ~ are cholsis of prefe-; 30 ~; rence: among ~; 4-hydroxyindol ~ e, 4-hydroxy: 5 ~ -methoxy-ndole, ~ 4-hy-roxy 5-ethox ~ lndole, ~ S-hydroxyindole, :; :: - 4 - ~

~ o ~ 3 ~ 7 ~ 7 2-carboxy S-hydroxyindole, 5-hydroxy 6- ~ methoxy-indole, 6-hydroxyindole, 6-hydroxy 7-methoxyindole, 5-methoxy 6-hydroxyindole, 7-hydroxyindole, 5,6-dihydroxyindole, l-methyl 5,6-dihyclroxyindole, 2-me-thyl 5,6-dihydroxyindole, 3-methyl 5,6-dihydroxy-indole, 2,3-dimethyl 5,6-dihydroxyindole, (5 or 6) -acetoxy (6 or 5) -hydroxyindole.
The particle size of these particles is generally slightly greater than 0.01 micron and is pre ~ erence between 0.01 and S0 microns and in particular between 0.1 and 20 microns.
They are preferably spherical.
The polymers which can be used according to the invention are essentially insoluble polymers in the ; reaction medium ~ in which the reaction takes place oxidation and are preferably chosen from natural or synthetic, organic or organic polymers nics, cross-linked, crystalline or amorphous, having a molecular weight between 5,000 and 5,000,000, defined below.
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The essentially insoluble character of polymer is justified by reasons essentially economical insofar as ~ the melanin pigment must be fix on a solid particulate support, to form the product according to the invention.
Solubility ~ of polymers in the environment reaction must not exceed ~ preferably 10%.
~ These ~ natural or synthetic polymers are `~ ~ chosen from:

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7 ~ S7 a) polymers derived from keratin which are in particular chosen from animal keratins or human, from, for example, selected materials among the hair, wool, skin, hair, bristles, feathers, scales and more particularly hooves, horn.
These materials are preferably washed and / or degreased, then reduced to particles.
Other polymers derived from keratin are chemically modified keratins having a weight molecular between 10,000 and 250,000, and in part the partially hydrolyzed keratin (or hydrolyzate keratin), obtained from skins that are rich in products with a molecular weight included between 50,000 and 200,000. This hydrolyzate is preferably obtained by moderate alkaline hydrolysis.
Prodults of this type are for example sold under the trademark KERASOL by the CRODA Company.
~ ~ Other modified keratins are keratins ; ~ 20 sulfonic molecules with a molecular weight between 10,000 ~ and l00,000, obtained from goose or chicken feathers :
or more advantageously encox of hooves or horn.
This keratin ~ es ~ t obtained by oxidation of all or ~ part of the disulfide bonds of the groupings-ts cystine ~ from keratin ~ in cysteic acid groups:
5O3H ~ 'oxidation;being; advantageously carried out in acid medium, such as formic acid, using a oxidizing agent, such as oxygenated water.

b) Sole fibroin.
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z ~ a7 ~ 7 c) Polymers derived from chitin: they are made up of chitin which is a polymer natural, the most important source of which is found in the shell of crustaceans, such as crabs, lobsters, lobsters, etc ... The chitin is prepared according to a proce-described, in particular, in the work of RAA MUZZARELLI
"CHITIN", published by PERGAMON PRESS OXFORD, 1977, pages 89-100 and 207-217. We can also use its drift deacetylated known under the name of chitosan, obtained by saponification of the acetyl groups of chitin.
Chitosan, as sold commercially, is particularly acetylated and contains 70 to 90 ~ by weight `of chitosan. It can also be used in the form of its insoluble salts, such as sulfates and phosphates.
Products of this type are sold for example under the trademark KYTEX by the company HERCULES.
~.
~; ~ d) Synthetic polymers are chosen among: ~ ~
; (i) crosslinked polymethyl methacrylate, such as the product ~ sold under the trademark ~ MICROPEARL M 305 by SEPPIC;
; ~~ (ii) cross-linked poly- ~ -alanine, such as ; déclt ~ e ~ dans ~ le; French patent No. ~ 2,530,250, or presented ~ advantageously in the form of microspheres having a very small size disperslte, 85 ~ in ; polds ~ having a particle size between 28 and 46 ml ~ crons. ~ These ~ poly- ~ -alanines are obtained according to a p; rocédé consists; ant to polymerize between 60 and 100C, and preferably around 80 C, of ~ acrylamide in a mixture of 30 ~ ~ t-butanol / toluene solvents, ~ in ratios included :::
~ between 1:24 and 10: 1 and preferably between 1: 6 and 6: 1, in , ~
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`presence of a polymerization initiator, a copoly-mother octadecene-maleic anhydride as suspending agent sion, then to submit the suspension of poly- ~ -alan.ine obtained on crosslinking using a dialdehyde, such than glutaraldehyde.
The polymerization initiator is preferred.
that of sodium or potassium tertiobutylate ~ 0.1 to about 2 mole% compared to acrylamide).
Glutaraldehyde is used as a aqueous solution between 20 and 25% and in a proportion between 1 and 15% by weight and pre ~ erence between 1 and 8% by weight relative to the weight of acrylamide of : departure;
; (lii) hollow microspheres of a copolymer vinylidene chloride and acrylonitrile, sold under .
~ the ~ trademark ~ EXPANCEL by ~ the KEMA NORD Company;
:
: (iv ~ porous polyamide microspheres 12d polyamide 6 or copolyamide 6 / I2, sold under the `::
~: trademark ORGASOL by the ATO-CHIMIE Company. These ~:::
mtcrospheres preferably have a particle size included ~: between ~ 10 and 50 microns; ~
~:: (v) ~ silicone powders which are erasers, resins and more particularly elastomers res ~ organopolysiloxanes.
: The products according to the invention are ; prepared according to a procedure consisting essentially of mix ~: 1 '~ air and; ~ a temperature preferably ; amb ~ lante and can ~ go] up to ~ lQ0C, the c; omposed ndolic ~ of ~ formula (I ~: and the ~ particles of polymers : 30 described above, in an essentially non-soIvant of the polymer, as die ~ ini above.
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2C ~ 3S7 If other oxidizing agents are not used as the oxygen in the air, we operate at a preEerence pH
alkaline, in which case the pigment gradually forms and attaches to the particle surface and / or in the network or the pores thereof. We can also use in presence of oxygen a metallic oxidation catalyst such as the cupric ion.
These products can also be prepared in proceeding to an immediate formation of the melanin pigment, using an oxidizing agent such as hydro peroxide gene, periodic acid and its water-soluble salts and derivatives, permanganates and dichromates, such as from sodium or potassium, sodium hypochlorite, potassium ferricyanide, ammonium persulfate, silver oxide, ferric chloride, lead oxide (Pb IV), sodium nitritei by addition of iodide and hydrogen peroxide, iodide being preferably one alkali, alkaline earth metal or ammonium iodide.
These oxidizing agents can be activated ~,. .
optionally with a pH modifying agent.

~ For products intended for an application . ~. .
cosmetic, preferably used as oxidizing agents hydr ~ ogene peroxide, periodic acid and its salts, e potassium permanganate ~ um, sodium hypochlorite ammonium persulate, sodium nitrite and system iodide / hydrogen peroxide.
The order of addition of the components involved in the preparation of the product, according to the invention, little importance on the condition that one incorporates in ; last place the oxidizing agent when it is used g _ Z ~ 7 ~ 7 without pH modifying agent, and in the case of the system iodide oxidizer / hydrogen peroxide ~ we introduce last place, either hydrogen peroxide or iodide.
In the case where a modifying agent is used pH meter to activate the oxidizing agent, we pre ~ era lastly add either the oxidizing agent or the pH modifying agent.
When using a keratin hydrolyzate, the medium pH should preferably be less than S, so avoid the solubilization of the modified keratin.
When using sulfonic keratin, the medium is either essentially alcoholic or aqueous, in which case the pH should be less than 7.
When using chitosan, the medium aqueous should preferably have a pH higher than 5.8.

.
As indicated above, the reaction medium :
is a substantially non-solvent medium of the polymer considered. It is preferably made up of water and it can possibly consist of a mixture of water and solvent, ~ sol ~ vant etan-t chosen from alcohol ethyl, isopropyl alcohol, tert-butyl alcohol that the monomethyl, monoethyl, monobutyl ethers as ethylene glycol ~, monoethyl ether acetate ~.
~ ethylene glycol. ~ ~
,, These solvents must, moreover, be able solubilize the indolic dye.

When the medium is CQnStitUé by a mixture water-solvent (s), solvents are present in con-preference centers between ~ 0.5 and 90 ~ in : ~:
: ~ `:: :::

~ - 10 -~:::.

ZC ~ 37 ~ 7 weight relative to the total weight of the composition, and particular between 2 and 50% by weight, and preferably between 2 and 20 ~ by weight.
Their nature is chosen and their proportion is adjusted according to the solubility criteria of the derivatives indole and the insolubility criterion of the polymer.
In the process according to the invention, preferably use the indolic dye dan.s des weight proportions between 0.1 and 10% and preferably between 1 and 5% by weight, the polymer represents both 0.05 to 50% by weight and preferably 4 to 30 ~ in ~
weight, the rest of the reaction mixture generally being consisting of water or a water / solvent mixture.
The oxidants are used in sufficient to oxidize the indolic dye and form the metal base.
When using the iodide ion to form the melanin pigment, this is preferably used in proportions of 0.07 to 4 ~ and in particular between ~ 0 ~, 7 to 3%, observing an indolic dye / I ratio between 0.6 and 6.
The ~ proportions are determined relative to the weight of the mllleu ~ r ~ eactlonnel. ~
For the preparation of the particles of polymer comprising a melanin pigment, a pigment ~ natural melanlque or; synthetic prepared with prealable ~ which ~ is; fixed ~ to the ~ surface of the particles or is absorbed by ~ these. ~ In this case, the melanin pigment finely ~ dlvise is dlspersed in a non-solvent medium of the polymer. After absorption of the pigment, the particles are dried.

- 1 1 -: ~ ' ::: -~::.::, ; ~ Q ~ 357 The product in the form of particles is used preferably in the cosmetic area in which it is preferably in the spherical form. he can be added in conventional cosmetic media to a concen-tration preferably between 0.2 and 35 ~
by weight, and more particularly between 2 and 20% by weight, relative to the total weight of the composition, for lead to protective cosmetic compositions of the human epidermis, make-up products, in particular eyelashes, eyebrows or skin, such as blush eyeshadows, blushers, liners still called "eye-l1ners", mascaras for eyelashes and eyebrows, or still dye compositions for hair. These cosmetic supports are known in themselves.
These compositions can be presented under form of lotion, thickened lotion, gel, cream, milk, powder, stick and possibly be condi-tionnees e ~ n aerosol: and be in the form of foam.
When the compositions are used for the ; 20 ~; ~ make-up of ~ skin, eyelashes and eyebrows, they may in particular be in solid form or pasty ~ anhydrous ~ or aqueous, such as oil emulsions in-water or ~ water-da ~ ns-hu ~ island; or ~ suspensions. These c ~ ompos1: tions have the advantage of being stable and present: good innocuity.
When ~ the compositions are used for the protect ~ ion: ~ of the ~ human epidermis against UV radiation, they therefore constitute ~ so-called composit1ons "solar",: ~ they can be in the form of su: spensions or: dispersions in solvents or .
~ - 12 -::

~ 379 ~ 7 fatty substances, in the form of emulsions - such as creams and milks, ointments, gels, solid sticks or aerosol foams.
In any case, when used in the form of emulsions, they may also contain surfactants well known in the art technique, chosen from anionic surfactants non-ionic, cationic or amphoteric.
The makeup compositions and the compositions : solar ions can also contain fatty coxps, organic solvents, silicones, thickeners, softeners, sun filters, anti-aging agents foams, moisturizers, perfumes, preservatives anti-oxidants, fillers, seques-: trants, treatment agents such as copolymers anionic, cationic, nonionic amphoteric, as well ~ ~.
that their mixtures, propellants, alkaline agents : healthy or acidifying.
The fatty substances can be constituted by a ~ oil or a wax or a mixture thereof, fatty acids, fatty alcohols, petrolatum, paraffin, lanolin, ~ hydrogenated lanolin, acetylated lanolin.
The hulles are chosen first among animal hulles ~, vegetable, mineral or synthetic and in particular hydrogenated palm oil, castor oil : hydrogenated,: vasellne oil,: paraffin oil, Purcellln oil. ~
The waxes are ~ preferred among the : wax; s an ~ males, fQssi: the, vegetable, mineral or; synthe-

3 ~ 0 ticks ~ among which we can cite waxes ~ `
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~ Z ~ 6) 7 ~ S7 bees, Carnauba, Candelilla, cane waxes sugar, from Japan, ozokerites, Montan wax, microcrystalline waxes, paraffins.
The compositions can also contain plus ultra-fine particles with pigmen-ts melanic, as defined above, others pigments generally used in cosmetics, in particular pearlescent pigments which still make it possible to vary the colors likely to be obtained.
The following examples are intended to illustrate the invention without presenting a characteristic limiting.

We prepare a polymer and pigment powder melanic by adding, successively with stirring magnetic, in a beaker, the following ingredients:
Poly-B-alanine cross-linked at 3 ~ (approx.
~ 2 microns) 4.9 g - 5,6-dihydroxyindole 1.0 g ~ 20 - Water ~ 91.4 g - ~ - Sodium nitrate 2.7 g HCl (1 N) qs p ~ = 4 After filtration, washing with water and then ethyl alcohol ~ lique, we obtain a black ultrafine powder.

We prepare a polymer and pigment powder melanlque by adding, successively with stirring magnetlque, ~ dan ~ s ~ a beaker, the following ingredients:

6-hydro; xyindole 1.7 g 30 ~ Alcohol ~ ethyl ~ 13.2 g Water 59.5 g :: ~: ~. ...
~ 14 -:::
: ~:

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--:. -,:. . ,,:, -:

7 ~

- Ammonium iodide 1ll g Crosslinked Poly- ~ -alanine (granuloma-sort included between 0.1 and 1 micron) 9.9 g - H202 (20 volume aqueous solution) 4.6 g After filtration, washing with water and then ..
ethyl alcohol, an ocher ultrafine powder is obtained red ~

A chitomelanic compound is prepared as an addi-working, successively with magnetic stirring, in a beaker, the following ingredients:
- 5,6-dihydroxyindole 1.5 g - Ethyl alcohol 12.4 g - Water 73.1 g - Potassium iodide 0.7 g : - Chitin extracted from carapaces of shellfish, sold under the brand of CHITIN LS 2970 trade by the Company .
: Nancy Seroblological Laboratory1.6 g 20; - Aqueous solution of hydrogen peroxide at 30 volumes ~ 10.7 g : The pigment is formed upon the addition of , ~
oxidant:: ~
After filtratlon, ~ wash with water and then : ethyl alcohol: ic, we obtain a black ultrafine powder.

: We ~ prepare ~ a ~ chitomelanic compound in addi-:: -working, successively with magnetic stirring, in : a beaker, the following ingredients:
- 5,6-dihydroxyindole: l,: L g :
~ - Water ~ 96.0 g i ~. :,:. ::. . . . .. ~:

2 ~) 7 ~ 357 - Chitin extracted from carapaces of shellfish, sold by Socie-te Nancy Serobiological Laboratory under CHITIN LS 29701.9 g - Sodium periodate 1.0 g The pigment is formed from the addition of the oxidant.
After filtration, washing with water and then ethyl alcohol, we get a black ultraflne powder. .

We prepare a chitomelanic compound as an addi-working, successively with magnetic agitation, in a beaker, the following ingredients:.
- 6-hydroxyindole 2, ag - Ethyl alcohol 24.9 g - Water 69.2 g ~ -: ~ Chitin extracted from carapaces of ~. ~
shellfish, sold by the Company Serobiological Laboratory ~ Nancy 20 ~ sous: the trademark CHITIN LS 2970 1.4 g Ammonium persulfate 1.7 g :: The pigment forms ~ upon addition of the oxidant.
After filtration, wash with water then:
: ethyl alcohol,: we obtain a powder: ultrafine wine tint.
: EXAMPLE 6 We prepare a chitomelanic compound in ~ addi-strung, ~ successively ~ under magnetic stirring, in a beaker, the following ingredients:
5-meth ~ oxy 6-hydroxyindole ~ ~ 0, S g , : - 16 -, 2 ~ q957 - Ethyl alcohol 31.7 g - Water 63.4 g - Chitin extracted from carapaces of shellfish, sold by the Company Nancy Serobiological Laboratory under the trade name CHITIN LS 2970 0.9 g - Potassium permanganate in 1 N aqueous solution: 3.2 g 0.51 g MA
The segment is formed as soon as the oxidant.
After filtration, washing with water and then ~ ethyl alcohol, an ultrafine purple powder is obtained ; ash mauve. ``

A chitomelanic compound is prepared as an addi- -tionnant, ~ successively with magnetic stirring, in ~ a ~ beaker, the following ingredients:
. ~ ,: '. : ::
2 ~, 3-dlmethyl 5,6-dihydroxyindole hydrobromide 3.0 g ; 20 - Ethyl alcohol ~ 27.6 g - Water 66.3 g -ChltiDe shells of ~;
~ crustaceans ~, sold by the ~ Company s ~ Serobiological Laboratory of ~ Nancy under the trade name CHITIN LS 2970 1.7 g Sodlum nitrite ~ ~ 1.4 g The powder u] trafine, ~ after filtration, washing at eu pU15 with alcohol, e ~ t telnte ~ mauve.

:, ~:,. : -Z (~ 7 We prepare a chitomelanic compound in mixing, with magnetic stirring, the compounds following:
- Chi-tosane sold under the brand of KYTEX M trade by HERCULES 10.7 g Water alkalized by NaOH
Water 75.9 g NaOH 1.4 g - 5,6-dihydroxyindole 1.7 g Ethyl alcohol 10.3 g With chitosan powder suspended in alkaline water, add 5,6-dihydroxyindole in solution in ethyl alcohol. We separate the precipitate black obtained by filtration, washing with water, then ethyl alcohol .:
:: EXAMPLE 9 .
We prepare a keratino-melanic compound in ~: adding, successively with magnetic stirring, ~:::
in a beaker, the following ingredients:

- Keratine (lava brown hair and ... .
: powdered) 2.1 g ~ -::: ~: ~
5.6 ~ dihydroxyindole ~ 0.8 g - Ethyl alcohol ~ 21.1 g - Water ~: ~ 76.0 g : The reaction to air is left by ~ area (15 minutes) before filtering the beige gray ultrafine powder:

M :: obtained.

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We prepare a keratino-melanic compound in adding, successively with magnetic stirring, in a beaker, the following ingredients:
- 5,6-dihydroxyindole 1 ~ 0 g - Ethyl alcohol 24.4 g - Water 57 0 g - Keratine (lava brown hair and powdered) 1.3 g 10 - NaOH in 1N aqueous solution (16.3 g) 0.65 g MA
After filtration, washing with water is obtained then with ethyl alcohol, a gray ultrafine powder way.

: We prepare a keratin-melanin compound by 1::
~ adding, successively with magnetic stirring, ~:
.i:. .
~: in a beaker, the following ingredients:

: - Keratin (washed white hair and : reduced to powder) ~ ~: 0.8 g 20: - 7: -hydroxy ~ lndole: ~ 1.0 g : - Potassium iodide: 1.0 g i - Ethyl alcohol ~ 14.0 g Water ~ 69.2 g H2O2 ~ (solutlo ~ n aqueous at 30 volumes) ~ 14.0 g ~;
:;:: We obtain ~ after ~ thread: tration, washing with water pUlS ~ with ethyl alcohol, u ~ e very brown ultlafine powder dark.
EXAMPLE 12: ~:
:. Qn: prep ~ re a ~ keratin-melanin compound in adding ~, successively: under magnetic agltation, in a ~ b8cher, the following ingredients :
i; ~;

- Keratin (washed white hair and powdered) 1.9 g

- 4-hydroxyindole 1.2 g - Ethyl alcohol 23.1 g - Water 70.1 g - Sodium periodate 3.7 g The pigment is formed upon the addition of the oxidant. ~;
After filtration, washing with water and then 10 ethyl alcohol, you get a black ultrafine powder -bluish. - ~

We prepare a ke ~ atino-melanique compound in adding, successively with magnetic stirring, .
in a beaker, the following ingredients ~
; Kbratlne ~ lava brown hair ~ and powdered) ~ 1.4 g

5 ~ -methoxy 6-hydroxyindole 2.8 g Ethyl alcohol ~ 41.7 g 2 ~ 0 - ~ Water ~ 51.4 g - Potassium permang ~ anate (aqueous solution ~ l ~ N ~: ~ 2.7 g) ~ 0.43 g MA
The ~ p ~ lgme ~ nt is ~ formed from ~ additlon the ox ~ ydant.
After filtration, wash with water and then alcoo ~ l ~ éthyllque, ohtlent an ultrafine black powder.

A keratino-melanic compound is prepared by adding, ~ sUcCesS1vement under magnetic agltation, 30 ~ in ~ a ~ beaker ~ the following ingredients - Keratine (lava brown hair and ,,: ~::
.: ... .,. :. :, -,.: ,,:::

powdered) 1.1 g

- 6-hydroxyindole 1.1 g - Ethyl alcohol 22.0 g - Water 74 7 g - Ammonium persulfate 1.1 g The pigment is formed from the addition of the oxidant.
After filtration, washing with water and then ethyl alcohol, we obtain a black ultrafine powder.

We prepare a keratino-melanic compound in adding, successively with magnetic stirring, in a beaker, ~ es following ingredients::
- Keratin (washed white hair and powdered) ~ 1.0 g 3-methyl 5,6-dihydroxyindole: 1.0 g - Ethyl alcohol 9.8 g ~
Water: `87.6 g Sodium ni ~ trite ~ 0.6 g 20; ~ - HCl ~ (l N):; ~ qs pH = 4.9 The: ~ pigment ~ is formed upon the addition of ::
: ~:
the oxidant. : ~::
After ~ ès ~ f ~ lltratlon, ~ washing ~ with water and then:
Ethyl alcohol, ~ an ultrafine brown powder is obtained.
:: EXAMPLE 16 :: We prepare a ~: keratino-melanic compound in adding, ~ successlvement under magnetic agltatlon, in ~; a beaker ~ the ~ lngredlents auivants ~
- Ke: terry: (hair b ~ launches washed and:: ~
reduced ~ powdered ~ 3.2 g 4-hydroxyindole ~ ~ 3.2 g ~: ~

~ - 21 -:,:
, ~ -:

- Ethyl alcohol 32.0 g - Water 60, ~ g - Sodium periodate 0.8 g The periodate is formed upon the addition of the oxidant.
~ after filtration, washing with water and then ethyl alcohol, we obtain a gray ultrafine powder ~
medium blue. :

We prepare a keratin-melanin compound in adding, successively with magnetic stirring,. ~::
in a beaker, the following ingredients:
- Keratine (washed white hair and powdered) 1.0 g - 5-hydroxyindole 1 r 7 g - Ethyl alcohol 9.8 g -..:,.
- Water. 86.5 g - Ammonium persulfate I, 0 g :
:.
: ~ The pigment is formed from the addition of the oxidant.
.
After filtration, wash with water for ethyl alcohol, you get an ultrafine brown powder ollve ~

We prepare a keratino-melanic compound in ~:. ::
adding, successively under magnetic stirring, : in ~ a ~ beaker, the following ~ lngredients:
. ~
: - Sulfonic keratin (from ~ hooves 'of cattle): 4.3 g ; 30 - 5,6-dihydroxyindole o, gg - Sodium iodide o, gg ;

~ - 22 -:

z ~ q9 ~ i7 - Ethyl alcohol 87.0 g - H2O2 (aqueous solution at 30 volumes) 2.2 g The pigment forms as soon as the peroxide is activated hydrogen.
After filtration, washing with water and then ethyl alcohol, we obtain a black ultrafine powder.

We prepare a keratino-melanic compound in adding, successively with magnetic stirring, 10 in a beaker, the following closlents ~
- Sulfonic keratin (from hooves cattle) ~ 6.1 g - 6-hydroxyindole 1.8 g ; - Ammonium iodide ~ 0.4 g ; ~ - Ethyl alcohol ~ 81.9 g H2O2 (solutlon ~ aqueous 3 ~ 0 volumes) ~ 9.8 g The pigment forms as soon as the peroxide is added hydrogen. ~
After ~ flitrat1on, washing with ethyl alcohol ~, 20 ~ on ~ obtains a ~ dark brown ultrafine powder.
EXAMPLE? 0 Preparation ~ of ~; cross-linked poly- ~ -alanine.
In ~ a ~ reacte ~ ur of 3 liters, provided with ~ a stirred ~
teur ~ type "anchor" with a diameter of 90 mm, an arrival a ~ ote, ~ a ~ ampou ~ the ~ addition and a column head ; to ~; dls ~ tlller, ~ we ~ introduced ~ 934 g of toluene, ~ 1666 g ~ of ter-tlobutanol ~ and ~ 1.4 g ~ of maleic anhydride copolymer / -octade ~ cèné sold under the ~ trademark PA-18 by ~ la ~
Soci; ete ~ GULF. ~ After heating ~ fage of this ~ mixture at 70C, there 3Q; ~ aioute 10 ~ 0 g of acrylamide. We then bring the temperature to 100C and 120 ml of azeotropic mixture are distilled `: ~
~ - 23 -:. ... ,. . . ,. ,. , ..:

2 ~ 3 ~ 791S7 water / toluene / tertiobutanol. After the end of the distill-tion, the reaction mixture is cooled to 80C, and adjusts the stirring speed to 550 rpm. We add then in 10 minutes a solution of 2.24 g of tertiobuty-potassium late in 40 g of tert-butanol. The light bulb addition is rinsed with 120 ml of toluene. After 7 stirring hours at 80 ° C., allow to return to temperature ambient. Then add to the mixture, drop by drop,

7.5 ml 12N hydrochloric acid 10A suspension of the microspheres obtained, ~ add under vigorous agitation (550 rpm), at 50C, 100 ml of water in 15 minutes, then 15 ml of a gluta- solution raldehyde to 25 ~ in 20 minutes. After maintaining stirring for 4 hours at this temperature, let return to room temperature. After decanta-: tion, the supernatant solvents are eliminated and the microspheres: are washed twice with 500 ml of ethanol.
Spinning after ~ each wash is ef ~ done by centrifu-g ~ tion (3500 rpm). One wash per 15 liters: water is 20 ~ ensul ~ te: carried out in con: tlnu, then the water ~ is eliminated up to a ~ lnal volume of mixture of 600 ml.
The po ~ ly ~ - ~ -alanine crosslinked is then dried by lyophilis ~ ati ~ on: and we obtain ~ ient 92 g of white powder whose di ~ ameter ~ of mlcrospheres is on average 0.37 +
0.2 ~ mlcrons ~
} Eticulation rate, i.e.
: gl ~ utaraldehyde / acrylamlde contribution, is approximately 3%.

:
24:
'': -~.,. . , -.
. . ,. ,,,., -,. :.
. -,. . . . . .

~ 79 ~ 7 (II) Preparation of particles comprising the pigment melanic Operating mode (IIa) 0.55 g of 5,6-dihydroxyindole are dissolved in 4Q g of water, then it is adjusted to pH: 9 with a solution of NaOH (1 N). 10 g of the prepared microspheres are introduced into it next (I) soaked in a few drops of ethanol. We heats to 40C, then agitates on a rotary evaporator for 40 minutes. A colorless dispersion is obtained. We intro 1.25 g of CuSO4 ~ 5H2O dissolved in 10 g of water.
In the suspension, brown in color, it is bubbled oxygen for 2 hours. Blackened microspheres are left stirring overnight at the temple rature ambient, under oxygen atmosphere, then washed until ~ that the washings are colorless and neutral; the particles are dried by lyophilization.
Operating mode (IIb) a) 40 g ~ of ~ microspheres prepared according to are ~ swollen ~ with a solution consisting of 10 g of 20 ~ CuSO4-5H2O ~ and ~ 4 ~ 00 g ~ of water- The mixture is put under stirring for 1 hour ~ at room temperature, then :
; lyophilize.
:; b ~) 0, 2 ~ ~ g ~ of ~ 5,; 6-dihydroxylndole are dissolved in ~ 80 g ~ of water, pulS is added to pH: 9 by a solutlon of ~ NaOH ~ In ~ this ~ solution, disperse 20 g of prepared microspheres ~ above (a). Oxidation of the suspenslon ~ noircl ~ e ~ edt ~ completed solvent mode opera-oire ~ a ~

, ~ 25 -) 7 ~

A polymer and pi.gment powder is prepared:
melanic by adding, successively with stirring magnetic, in a beaker, the following ingredientsc:
- 5,6-dihydroxyindole 5.0 g - Ethyl alcohol 6.6 g - Polyméthacryl ~ te de methyl reticule, sold under the trademark MICROPEARL
M 305 by the company SEPPIC 3.7 g 10 - Ammonium persulfate 1.5 g - Water qs 100.0 g After filtration, washing with water and then alcohol, you get a very dark gray ultrafine powder. .
EXAMPLE 22. : -; ~ We prepare a polymer and pigment powder ~ ~ melanique by adding, successively with stirring : magnetic, in a beaker, the following ingredients:
S, 6-dihydroxyindole ~ ~ 11.1 g ~ Ethyl alcohol: 16.7 g 20 - ~ Water Polyamide 12 sold under the brand of ORGASOL 2002 D Natural trade by ~;
Socl ~ summer ~ ATO-CHEMISTRY ~ ~ 11.1 g Pure NaOH: 5.6 g We lalss; e parPalre the reaction to air ~ 4 h ~ eures) before: de: f: filter; the ultrafine black powder obtained that ~ separated ~ by filtration, washing with water, then alcohol.

~ ': `:
. .
,::
~ 26 -::
. . .

We prepare a polymer and pigment powder melanic by adding, successively with stirring magnetic, in a beaker, the following ingredients:
- 5,6-dihydroxyindole 11.1 g - Ethyl alcohol 16.7 g - Water 55.5 g - Vinylidene chloride copolymer /
acrylonitrile in the form of a microsphere, sold under the trademark EXPANCEL 551 WU by the company KEMA NORD 11.1 g - pure NaOH 5.6 g Let the reaction perfect in air (1 hour) before filtering the very fine gray ultrafine powder dark obtained which is separated by filtration, washing with water, .:
then alcohol.

A coloring composition is prepared for ;: ~ treatment of white hair, by mixing 20 ~ lngredlents sulvant : ~: -: Product prepared according to example 20 ~ ~
(IIa or ~ IIb) ~ 1.0 g Ac ~ ide ~ polyacrylic reticule, sold under :: the trademark ~ CARBOPOL 940 by the Soclet8 GOODRICH: ~ 0.7 g N-vlnylpyrrol1done-acetate copolymer ; de ~ vlnyle, ~ sold ~ by; ~ Société GAF sous ~:
the ~ PVP / VA-S-630 2.0 g trademark: ~
Ethanol ~ 17.0 g ; 30 - ~ Emulsion based ~ on cationic silicone ,: ~:
~:. -~: sold by DOW CORNING under the brand of :
~ - 27 ~

:

~) 795 ~ 7 trade DC 929 0.1 g - Triethanolamine qs pH = 6.6 - Water qs 100.0 g 5 g of this composition are applied to a lock of white hair. After drying, the hair is colors in a medium gray shade.

We prepare a mascara with the following composition:
- Triethanolamine stearate15.0 g - Candelilla wax 8.0 g. -- Carnauba wax 10.0 g - Hydroxyethyl cellulose 1.0 g - Gum arabic 1.0 g - Product according to example 18 8.0 g - Methyl parahydroxy benzoate 0.15 g Propyl parahydroxy benzoate 0.15 g . :
- Deionized water qs 100.0 g In this example, we can replace the product:
;
: from ~ example 18 with that of example 19.
20:; : EXAMPLE 26 ~ We prepare an eyeliner with the following composition : ~ boasts: ~
Propylene glycol ~ ~ 8.0 g Polyethylene glycol 5.0 g IsopIopanolamine ~ Myrlstate 3.0 g Xanthan gum: ~ 1.0 g Alcoo ~ l ~ polyvln ~ yllque: ~ ~ o, 5 g - Lanolin hydrogenee ~ ~ 4.0 g Parahydroxy ben ~ zoate de: methyl ~ 0,1 g - ~ Propyl parahydroxy benzoate o, lg : - Parahydroxy benzoate of e ~ thyle 0.1 g `::
: - 28 -~::::
~: ::
, ~

79 ~ 7 - Titanium mica 5.0 g - Black pigment (product according to Example 12) 7.0 g - Permuted water qs 100.0 g In this example, the prodult of example 12 can be replaced, for example, by those of examples 1, 3, 4, 6, 8, 11, 13, 14, 15, 18, 19.

We prepare a composition foundation next:
10 - Stearic acid 2.2 g - Glycerol stearate 3.2 g - Vaseline oil 4.0 g - Isopropyl palmitate g, og - 2-ethylhexyl palmitate 8.0 g : - Propyl parahydroxy benzoate: ~ 0.1 g ; - Triethanolamine 1.1 g - Glycerine: 3.0 g Propylene glycol 2.0 g : Alumino; magnesium sllicate ~ 1.0 g : 20 - ~ Carboxymethyl cellulose sodium 0.2 g - Imidazolldinyl urea ~ 0.3 g - Oxide ~ :: of: yellow iron ~ 2,0 g Red iron oxide ~ 1.4 y - Product according to ~ example 14: ~ 0.5 g Titanium dioxide: ~: 8.0 g Talc ~ 5.0 g - Perfume:: ~ o, 3 g Water; permuted ~ ~ qsp100.0 g In this example :, the product of example 14 can be ~ replaced by those of examples 2, 5, 9, 10, 11, .3,: 14 ,: 15, 20 or ~ 21.

, : ~: - 29 - ~::
. ~
.
.
~.
..:

Z ~ 10 ~ 7 We prepare a solar composition:
- Octyl-2 dodecanol-l 10.0 g - Magnesium stearate ~, 0 g - Beeswax 5.0 g ...
- Lanolin hydrogenated 1.0 g - Lanolin 4.0 g ; - Sorbitan sesquioleate sold under the ARLACEL 83 trademark by Company HERE 4.5 g - Mixture of glycerol monodistearate and potassium stearate (9317) 1.0 g - Vaseline oil 27.0 g - Product prepared according to Example 20 ~ (IIa) or (IIb) 5.0 g - Preservatives qs. .:
-: Perfume qs Water ~ qs 100.0 g In a beaker and with magnetic stirring, : ~ dissolves 1.34 g of 6-aminoindole in a solution consisting of 140 ml of water and 18 ml of alcohol.
The ~ pH ~ is adjusted to 6.3 with acetic acid diluted. ~ 9 ml of oxygenated water at 20 volumes are added.
::: ~,.
pu ~ s, ~ sOU9 nitrogen, 48.4 g of cross-linked poly- ~ -alanine prepared according to Example 20).
: The crosslinked poly- ~ -alanine is allowed to swell pen: for 2 hours, pU15: we have a drop by drop potassium iodide solution (0.75 g dissolved iodide in 7.5 cc of water) .. ~ ~

: ~ - - 30 - ~:
:

: ~ ::::,, 2 ~ 37 ~ 3S7 We maintain the brewing for 2 hours additional, then filtered and washed with water.
57.2 g of a black powder are obtained.

The following composition is prepared:
- Silk fibroin powder 10.0 g - 5,6-dihydroxyindole 1.0 g - Ethyl alcohol 20.0 g - H2O2 (20 volumes) `20.0 g 10 - Triethanolamine qsppH = 8 - Water qs100.0 g The ingredients are added one after the others under agitation. Fibroin staining silk begins when the pH is brought to 8 by triethanol-amine. The mixture is left under stirring for 1 hour.
The solution is therefore filtered on glass.
No. 4 (the filtrate is clear). The part recovered on filter glass is rinsed successively with water and 20 alcohol. ~ A powder obtained is dried. She is color -old-pink (pink-gray).
~ EXAMPLE 31 ~ - -::
The following composition is prepared:

Polydimeth ~ lsil ~ oxane powder, sold under ~ the ~ SILICONE trade mark OWDER X2-1605 by DOW CORNING 10.0 g 4-hydroxyindole ~ 1.0 g - Ethyl alcohol 10.0 g 22 (30 volume5) 10.0 g ; ~ 30 - Ammonia at 22 Be 10.0 g - Water qs100.0 g . .
`~ ~
~; - 31 -"` 2 ~ 79 ~ i ~

. . .

The pH of the solution is 10.6.
The ingredients are added one after the others, except monohydroxyindole which is previously disperses in alcohol.
The oxidative polymerization of indole begins this as soon as the ammonia is added.
The mixture is left under stirring for 10 minutes, then the solution is filtered with sintered glass No.

4.
The sintered powder is washed successively with water and alcohol until the washing juice is solt :: colorless. The dried powder obtained is gray in color:
darkens slightly blue. -.

`:::

~ 32 -::

Claims (79)

The embodiments of the invention, about which a exclusive right of property or privilege is claimed are defined as follows: - 1. Product made of polymer particles, characterized by the fact that the polymer particles are chosen from the group consisting of particles of:
(a) polymers derived from possible keratin-slightly modified;
(b) silk fibroin;
(c) polymers derived from possible chitin-deacetylated;
(d) synthetic polymers chosen from the group made up of:
(i) crosslinked polymethyl methacrylate, (ii) crosslinked poly-.beta.-alanine, (iii) hollow microspheres of the chloride copolymer vinylidene and acrylonitrile, (iv) porous microspheres of polyamide 12, of poly-amide 6 or copolyamide 6/12, and (v) silicone powders consisting of gums, resins, organopolysiloxane elastomers, said particles having a particle size less than 100 microns and comprising on the surface and / or in the polymer network, a natural melanin pigment or synthetic, this pigment being either previously formed and absorbed by particles, either formed in situ by oxida-tion of an indolic dye. 2. Product according to claim 1, characterized by the fact that the melanin pigment is a pigment resulting both from the oxidation of at least one indolic dye responding to the formula:

(I) in which:
R1 represents a hydrogen atom or a group C1-C4 alkyl pement;
R2 and R3, identical or different, represent try a hydrogen atom, a C1-C4 alkyl group, a carboxyl group or a C1-C4 alkoxy group carbonyl;
R4, R5, R6 and R7, identical or different, represent a hydrogen atom, an alkyl radical in C1-C4, a group -NHR (in which R denotes an atom hydrogen or C1-C4 alkyl, hydroxy-C1-C4 alkyl or C2-C4 polyhydroxyalkyl), acylamino, carboxyl, C1-C4 carboxyalkyl, C1-C4 alkoxy carbonyl, C1-C4 alkoxy C1-C4 carbonylalkyl, carbamyl, halogen, C1-C4 mono- or polyhydroxyalkyl, C1-C4 aminoalkyl, a group OZ, in which Z denotes a hydro-gene or a linear or branched C1-alkyl group C20, a C1-C4 aralkyl group, a group formyl or a linear C2-C20 acyl group or branched, a linear C3-C20 alkenoyl group or branched, a group -SiR11R12R13, a group -P (O) (OR8) 2, an R8OSO2- group; the radicals R4 and R5, either R5 and R6, or else R6 and R7 can form, together with the carbon atoms to which they are attached, a cycle possibly containing a group carbonyl, a thiocarbonyl group, a group or a group ;
provided that at least one of the radicals R4 to R7 represents an OZ group, or that one of the radicals R4 to R7 represents -NHR, or alternatively that R4 and R5, or R5 and R6, or R6 and R7 form a cycle, R8 and R9 represent a hydrogen atom or an alkyl group lower in C1-C4, R10 represents an alkoxy group C1-C4 or a mono- or dialkyl (C1-C4) amino group, R11, R12 and R13, identical or different, represent linear or branched C1-C4 alkyl groups;
or one of its alkali metal salts, alkaline earth, ammonium or amines. 3. Product according to claims 1 or 2, charac-terrified by the fact that the particle size is greater than 0.01 micron. 4. Product according to claims 1 or 2, charac-terrified by the fact that the particle size is between 0.01 and 50 microns. 5. Product according to claims 1 or 2, charac-terrified by the fact that the particle size is between 0.1 and 20 microns. 6. Product according to claims 1 or 2, charac-terrified by the fact that the particles are spherical. 7. Product according to claim 2, characterized by the fact that the indolic dye of formula (I) is chosen from the group consisting of 4-hydroxyindole, 4-hydroxy 5-methoxyindole, 4-hydroxy 5-ethoxyindole, 5-hydroxyindole, 2-carboxy 5-hydroxyindole, 5-hydroxy 6-methoxyindole, 6-hydroxyindole, 6-hydroxy 7-methoxyindole, 5-methoxy 6-hydroxyindole, 7-hydroxyindole, 5,6-dihydroxyindole, 1-methyl 5,6-di-hydroxyindole, 2-methyl 5,6-dihydroxyindole, 3-methyl 5,6-dihydroxyindole, 2,3-dimethyl 5,6-dihydroxy-indole and (5 or 6) -acetoxy (6 or 5) -hydroxyindole. 8. Product according to claim 2, characterized by the fact that said polymers are essentially insoluble in the reaction medium in which the oxidation reaction takes place. 9. Product according to claim 1 or 8, charac-terrified by the fact that said polymers are networked crosslinked, crystalline or amorphous, and have a molecular weight area between 5,000 and 5,000,000. 10. Product according to claims 1, 2, 7 or 8, characterized in that the polymers derived from keratin are animal or human keratins, derived of materials chosen from the group consisting of hair, wool, skin, hair, bristles, feathers, scales, hooves and horn. 11. Product according to claims 1, 2, 7 or 8, characterized in that the polymers derived from keratin are keratins chemically modified by hydrolysis or oxidation and having molecular weight between 10,000 and 250,000. 12. Product according to claims 1, 2, 7 or 8, characterized in that the polymers derived from keratin are partially hydrolyzed keratins, obtained from hides and having a molecular weight between 50,000 and 200,000. 13. Product according to claims 1, 2, 7 or 8, characterized in that the polymers derived from keratin are sulfonic keratins, obtained from goose or chicken or hoof or horn feathers, and having a molecular weight between 10,000 and 100,000. 14. Product according to claims 1, 2, 7 or 8, characterized in that the polymers derived from chitin consist of chitin or its derivative deacetylated. 15. Product according to claims 1, 2, 7 or 8, characterized by the fact that the polymer particles are particles of crosslinked poly-.beta.-alanine. 16. Product according to claims 1, 2, 7 or 8, characterized by the fact that the polymer particles are hollow microspheres of chloride copolymers vinylidene and acrylonitrile. 17. Product according to claims 1, 2, 7 or 8, characterized by the fact that the polymer particles are porous microspheres of polyamide 12, poly-amide 6 or copolyamide 6/12. 18. Product according to claims 1, 2, 7 or 8, characterized by the fact that the polymer particles are porous microspheres of polyamide 12, poly-amide 6 or copolyamide 6/12, and by the fact that said microspheres have a particle size between 10 and 50 microns. 19. Process for preparing a product according to the claim 1, characterized in that one disperses the melanin pigment formed beforehand, under finely divided form, in a non-solvent medium of polymer and containing said polymer particles, and that after absorption of the pigment, the particles are dried. 20. Process for the preparation of a product such as defined in claim 2, characterized by the fact that the indolic dye of formula (I) and a particulate polymer charge, having particle size less than 100 microns and that then proceeds to the formation of the pigment by oxidation of the indolic dye. 21. Method according to claim 20, characterized by the fact that the indolic dye of formula (I) is chosen from the group consisting of 4-hydroxyindole, 4-hydroxy 5-methoxyindole, 4-hydroxy 5-ethoxyindole, 5-hydroxyindole, 2-carboxy 5-hydroxyindole, 5-hydroxy 6-methoxyindole, 6-hydroxyindole, 6-hydroxy 7-methoxyindole, 5-methoxy 6-hydroxyindole, 7-hydroxyindole, 5,6-dihydroxyindole, 1-methyl 5,6-di-hydroxyindole, 2-methyl 5,6-dihydroxyindole, 3-methyl 5,6-dihydroxyindole, 2,3-dimethyl 5,6-dihydroxy-indole and (5 or 6) -acetoxy (6 or 5) -hydroxyindole. 22. Method according to claims 20 or 21, characterized by the fact that the particle size of the charge polymer particle is greater than 0.01 micron. 23. Method according to claims 20 or 21, characterized by the fact that the particle size of the charge polymer particle is between 0.01 and 50 microns. 24. The method of claim 20 or 21, charac-terrified by the fact that the polymer is essentially insoluble in the reaction medium in which the oxidation reaction takes place. Method according to claims 20 or 21, characterized by the fact that the polymer is networked crosslinked, crystalline or amorphous, and has a molecular weight between 5,000 and 5,000,000. 26. Method according to claims 20 or 21, characterized in that the polymer is derived from animal or human keratin, from selected materials in the group consisting of hair, wool, skin, hair, bristles, feathers, scales, hooves and horn. 27. Method according to claims 20 or 21, characterized by the fact that the polymer is a keratin chemically modified by hydrolysis or oxidation and having a molecular weight of between 10,000 and 250,000. 28. Method according to claims 20 or 21, characterized by the fact that the polymer is a keratin partially hydrolyzed, obtained from hides, and having a molecular weight between 50,000 and 200,000. 29. Method according to claims 20 or 21, characterized by the fact that the polymer is a keratin sulfonic, obtained from goose or chicken feathers or hooves or horns, and having molecular weight between 10,000 and 100,000. 30. Method according to claims 20 or 21, characterized by the fact that the polymer is chitin or its deacetylated derivative. 31. Method according to claims 20 or 21, characterized in that the polymer is a poly-.beta.-crosslinked alanine. 32. Method according to claims 20 or 21, characterized by the fact that the particulate charge of polymer consists of hollow microspheres of copolymers of vinylidene chloride and acrylonitrile. 33. Method according to claims 20 or 21, characterized by the fact that the particulate charge of polymer consists of porous microspheres of polyamide 12, polyamide 6 or copolyamide 6/12. 34. Method according to claims 20 or 21, characterized by the fact that the particulate charge of polymer consists of porous microspheres of polyamide 12, polyamide 6 or copolyamide 6/12, and by the fact that said microspheres have a particle size between 10 and 50 microns. 35. Method according to claim 20, characterized by the fact that oxidation takes place slowly in air, at alkaline pH. 36. Method according to claim 20, characterized by the fact that the oxidation takes place by oxygen in presence of a metal catalyst. 37. Method according to claim 20, characterized by the fact that the oxidation is carried out by adding at least at least one oxidizing agent chosen from the group consisting of hydrogen peroxide, periodic acid and its salts, permanganates, dichromates, hypochlorite sodium, potassium ferricyanide, persulfate ammonium, silver oxide, ferric chloride, lead oxide (Pb IV) and sodium nitrite. 38. Method according to claim 20, characterized by the fact that the oxidation is carried out by adding a alkali, alkaline earth or ammonium iodide and hydrogen peroxide. 39. Method according to claim 20, characterized by the fact that the oxidation is carried out by adding at least at least one oxidizing agent chosen from the group consisting of hydrogen peroxide, periodic acid and its salts, potassium permanganate, sodium hypochlorite, ammonium persulfate, sodium nitrite and the system iodide / hydrogen peroxide. 40. Method according to claim 20, characterized by the fact that the reaction medium is an essential medium tally non-solvent of the polymer considered, consisting with water or a mixture of water and at least one solvent. 41. Method according to claim 40, characterized by the fact that the reaction medium is constituted by a mixture of water and at least one solvent, the solvent being present in a proportion between 0.5 and 90% in weight relative to the total weight of the composition. 42. Method according to claim 41, characterized by the fact that the proportion of solvent is understood between 2 and 50% by weight. 43. Method according to claim 42, characterized by the fact that the proportion of solvent is understood between 2 and 20% by weight. 44. Method according to claims 41, 42 or 43, characterized in that the solvent is chosen from the group consisting of ethyl alcohol, isopropyl alcohol pyl, tert-butyl alcohol, monomethyl ethers that, monoethyl, monobutyl ethylene glycol and ethylene glycol monoethyl ether acetate. 45. Method according to claims 20 or 21, characterized by the fact that the indolic dye of formula (I) is used in a proportion between 0.1 and 10% by weight, relative to the weight of the medium reactive. 46. Method according to claims 20 or 21, characterized by the fact that the indolic dye of formula (I) is used in a proportion between 1 and 5% by weight, relative to the weight of the reaction medium-nel. 7. Method according to claim 20, characterized by the fact that the polymer is used in a proportion from 0.05 to 50% by weight relative to the weight of the reaction mixture. 48. Method according to claim 47, characterized by the fact that the proportion of polymer is understood between 4 and 30% by weight. 49. Method according to claim 20, characterized by the fact that the mixing is carried out at a temperature between room temperature and 100 ° C. 50. Cosmetic composition, characterized by fact that it contains in a cosmetically medium acceptable, at least one product as defined in the claim 1. 51. Composition according to claim 50, character-laughed at by the fact that said product is present in a proportion between 0.2 and 355 by weight, relative the total weight of the composition. 52. Composition according to claim 51, character-laughed at by the fact that the proportion of product is between 2 and 20% by weight. 53. Composition according to claim 50, character-laughed at by the fact that the melanin pigment is a pigment resulting from the oxidation of at least one indolic dye responding to the formula:
(I) in which:
R1 represents a hydrogen atom or a group C1-C4 alkyl pement;

R2 and R3, identical or different, represent try a hydrogen atom, a C1-C4 alkyl group, a carboxyl group or a C1-C4 alkoxy group carbonyl;
R4, R5, R6 and R7, identical or different, represent a hydrogen atom, an alkyl radical in C1-C4, a group -NHR (in which R denotes an atom hydrogen or C1-C4 alkyl, hydroxy-C1-C4 alkyl or C2-C4 polyhydroxyalkyl), acylamino, carboxyl, C1-C4 carboxyalkyl, C1-C4 alkoxy carbonyl, C1-C4 alkoxy C1-C4 carbonylalkyl, carbamyl, halogen, C1-C4 mono- or polyhydroxyalkyl, C1-C4 aminoalkyl, an OZ group, in which Z denotes a hydro-gene or a linear or branched C1-alkyl group C20, a C1-C4 aralkyl group, a group formyl, a linear C2-C20 acyl group or branched, a linear C3-C20 alkenoyl group or branched, a group -SiR11R12R13, a group -P (O) (OR8) 2, an R8OSO2- group; the radicals R4 and R5, either: R5 and R6, or else R6 and R7 can form, together with the carbon atoms to which they are attached, a cycle possibly containing a group carbonyl, a thiocarbonyl group, a group or a group ;
provided that at least one of the radicals R4 to R7 represents an OZ group, or that one of the radicals R4 to R7 represents -NHR, or alternatively that R4 and R5, or R5 and R6, or R6 and R7 form a cycle, R8 and R9 represent a hydrogen atom or an alkyl group lower in C1-C4, R10 represents an alkoxy group C1-C4 or a mono- or dialkyl (C1-C4) amino group, R11, R12 and R13, identical or different, represent linear or branched C1-C4 alkyl groups;
or one of its alkali metal salts, alkaline earth, ammonium or amines. 54. Composition according to claims 50 or 53, characterized by the fact that the particle size of the cules is greater than 0.01 micron. 55. Composition according to claims 50 or 53, characterized by the fact that the particle size of the cules is between 0.01 and 50 microns. 56. Composition according to claims 50 or 53, characterized by the fact that the particle size of the cules is between 0.1 and 20 microns. 57. Composition according to claims 50 or 53, characterized by the fact that the particles are spherical. 58. Composition according to claim 53, character-laughed at by the fact that the indolic dye of formula (I) is selected from the group consisting of 4-hydroxy-indole, 4-hydroxy 5-methoxyindole, 4-hydroxy 5-ethoxyindole, 5-hydroxyindole, 2-carboxy 5-hydroxy-indole, 5-hydroxy 6-methoxyindole, 6-hydroxyindole, 6-hydroxy 7-methoxyindole, 5-methoxy 6-hydroxy-indole, 7-hydroxyindole, 5,6-dihydroxyindole, 1-methyl 5,6-dihydroxyindole, 2-methyl 5,6-dihydroxy-indole, 3-methyl 5,6-dihydroxyindole, 2,3-dimethyl 5,6-dihydroxyindole and (5 or 6) -acetoxy (6 or 5) -hydroxyindole. 59. Composition according to claims 50, 53 or 58, characterized in that the said polymers are cross-linked, crystalline or amorphous network, and have a weight molecular between 5,000 and 5,000,000. 60. Composition according to claims 50, 53 or 58, characterized in that the polymers derived from keratin are animal or human keratins, from materials selected from the group consisting of hair, wool, skin, hair, bristles, feathers, scales, hooves and horn. Composition according to Claims 50, 53 or 58, characterized in that the polymers derived from keratin are keratins chemically modified by hydrolysis or oxidation and having molecular weight between 10,000 and 250,000. 62. Composition according to claims 50, 53 or 58, characterized in that the polymers derived from keratin are partially hydrolyzed keratins, obtained from hides and having a molecular weight between 50,000 and 200,000. 63. Composition according to claims 50, 53 or 58, characterized in that the polymers derived from keratin are sulfonic keratins, obtained at from goose or chicken feathers or hooves or horn, and having a molecular weight between 10,000 and 100,000. 64. Composition according to claims 50, 53 or 58, characterized in that the polymers derived from chitin consist of chitin or its derivative deacetylated. 65. Composition according to claims 50, 53 or 58, characterized in that the particles of polymers are particles of crosslinked poly-.beta.-alanine. 66. Composition according to claims 50, 53 or 58, characterized in that the particles of polymers are hollow microspheres of copolymers of vinylidene chloride and acrylonitrile. 67. Composition according to claims 50, 53 or 58, characterized in that the particles of polymers are porous polyamide 12 microspheres, of polyamide 6 or copolyamide 6/12. 68. Composition according to claims 50, 53 or 58, characterized in that the particles of polymers are porous polyamide 12 microspheres, of polyamide 6 or copolyamide 6/12, and by the fact that said microspheres have a particle size between 10 and 50 microns. 69. Composition according to claim 50, character-laughed at by the fact that it is in the form of lotion, thickened lotion, gel, cream, milk, powder, stick and that it is possibly condition-born in aerosol. 70. Composition according to claim 50, intended to be used for make-up of the skin, eyelashes and eyebrows, characterized by the fact that it presents in solid or pasty, anhydrous or aqueous form. 71. Composition according to claim 50, intended the protection of the human epidermis against rayon-solar cells, characterized by the fact that it present as a suspension or dispersion in solvents or fatty substances or in the form of an emulsion, ointment, gel, solid stick or foam aerosol. 72. Composition according to claim 69, intended the protection of the human epidermis against rayon-solar cells, characterized by the fact that it present as a suspension or dispersion in solvents or fatty substances or in the form of an emulsion, ointment, gel, solid stick or foam aerosol. 73. Composition according to claim 70, intended the protection of the human epidermis against rayon-solar cells, characterized by the fact that it present as a suspension or dispersion in solvents or fatty substances or in the form of an emulsion, ointment, gel, solid stick or foam aerosol. 74. Composition according to claims 50, 69, 70, 71, 72 or 73, characterized in that it is present as an emulsion and it contains in addition to at least one anionic surfactant, not ionic, cationic or amphoteric. 75. Composition according to claims 50, 69, 70, 71, 72 or 73, characterized in that it additionally contains at least one cosmetic adjuvant acceptable chosen from the group made up of bodies oily, organic solvents, silicones, thick softeners, fabric softeners, sun filters, anti-foaming agents, moisturizing agents, perfumes, preservatives, antioxidants, fillers, sequestrants, treatment agents, propellants alkalizing or acidifying agents. 76. Composition according to claims 50, 69, 70, 71, 72 or 73, characterized in that it contains other pigments allowing to vary the coloring. 77. Application of a composition as defined in claims 50, 53, 58, 69, 70, 71, 72 or 73, protection of the human epidermis. 78. Application of a composition as defined in claims 50, 53 or 58 as a product of makeup. 79. Application of a composition as defined in claims 50, 53 or 58, for coloring human hair.